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Heavy metal dynamics at the sediment-water interface (SWI) has attracted plenty of attention due to their meticulous depiction for metal sorption-release processes. However, little is known about their concentration, migration and release characteristics underneath the ice, especially at the millimeter scale. Here we investigated dynamics of labile As, Cd, Cu, Mn, Pb and Zn by the diffusive gradients in thin-films (DGT) technique during ice-covered and ice-free periods in the Lake Xingkai basin. The concentrations of metals were relatively high at the SWI and ranged for As: 0.001~13.42 jmg L-1, Cd: 0.01~0.45 mg L-1, Cu: 0.001~2.75 mg L-1, Mn: 5.31~2958.29 mg L-1, Pb: 0.06~1.43 mg L-1, and Zn: 2.92~112.96 mg L-1. Particularly, concentration of Mn was extremely higher than other studies, possibly due to diagenetic process. Labile concentrations of heavy metals in January were significantly lower than those in May, suggesting that elevated temperatures lead to the release of heavy metals from the sediment to the overlying water. Based on the Fick's first law, the diffusive fluxes as a source of Mn (413.82-1163.25 mg-m-2d-1) and As (3.53 -8.12 mg-m-2d-1) indicated that heavy metals were released from sediments to the overlying water. While the diffusive fluxes as a sink of Zn (-1.80-(-2.36) mg-m-2-d-1) and Pb (-0.02-(-0.46) mg-m-2-d-1) to sediments. Redundancy Analysis (RDA) revealed that the main factors influencing the heavy metal migration were dissolved oxygen (45.6% of total explanation, P=0.01) in January, and water temperature (52.9%, P=0.006) in May. This study extends theoretical scope for understanding metal migration and release process, and provides valuable suggestions for lake management during the freezing period. [ABSTRACT FROM AUTHOR]

Heavy metal dynamics at the sediment-water interface (SWI) has attracted plenty of attention due to their meticulous depiction for metal sorption-release processes. However, little is known about their concentration, migration and release characteristics underneath the ice, especially at the millimeter scale. Here we investigated dynamics of labile As, Cd, Cu, Mn, Pb and Zn by the diffusive gradients in thin-films (DGT) technique during ice-covered and ice-free periods in the Lake Xingkai basin. The concentrations of metals were relatively high at the SWI and ranged for As: 0.001~13.42 μg L−1, Cd: 0.01~0.45 μg L−1, Cu: 0.001~2.75 μg L−1, Mn: 5.31~2958.29 μg L−1, Pb: 0.06~1.43 μg L−1, and Zn: 2.92~112.96 μg L−1. Particularly, concentration of Mn was extremely higher than other studies, possibly due to diagenetic process. Labile concentrations of heavy metals in January were significantly lower than those in May, suggesting that elevated temperatures lead to the release of heavy metals from the sediment to the overlying water. Based on the Fick’s first law, the diffusive fluxes as a source of Mn (413.82-1163.25 mg·m-2·d-1) and As (3.53 -8.12 mg·m-2·d-1) indicated that heavy metals were released from sediments to the overlying water. While the diffusive fluxes as a sink of Zn (-1.80-(-2.36) mg·m-2·d-1) and Pb (-0.02-(-0.46) mg·m-2·d-1) to sediments. Redundancy Analysis (RDA) revealed that the main factors influencing the heavy metal migration were dissolved oxygen (45.6% of total explanation, P=0.01) in January, and water temperature (52.9%, P=0.006) in May. This study extends theoretical scope for understanding metal migration and release process, and provides valuable suggestions for lake management during the freezing period.

Mercury (Hg) is a toxic, non-essential element for living organisms, frequently present in high concentrations in soils from industrial areas. The total, dissolved, and labile Hg concentrations in garden soils and their accumulation in edible vegetables (onion, garlic, lettuce, and parsley) grown on contaminated soils in localities situated a former mining area were evaluated. The labile Hg fraction was estimated by diffusive gradient in thin films (DGT). The soil-to-vegetable transfer factors, as well as the health risk by exposure to Hg, were calculated based on the labile Hg concentration in soil. The total Hg concentration in soil varied widely (0.11–3.77 mg kg−1), Hg in soil solution ranged between 2.14 and 20.2 μg L−1 and labile Hg between 1.13 and 18.6 μg L−1. About 36–96% (84% on average) of the Hg concentration in soil solution was found in labile form. Multivariate analysis revealed significant correlations between the labile Hg concentration in soil and Hg accumulated in vegetables. The hazard indices showed that, although the study area is affected by legacy pollution, exposure to soil and consumption of locally grown vegetables do not pose health risks. [ABSTRACT FROM AUTHOR]

Trace elements can have a wide variety of effects on microbial populations and their function in the aquatic environment. However, specific impacts on chemical and biological processes are often difficult to unravel, due to the wide variety of chemical species involved and interactions between different elemental cycles. A replicated mesocosm experiment was used to test the effect of increasing copper concentrations, i.e., from 6 mg kg−1 to 30 and 120 mg kg−1, on nitrogen cycling in a freshwater sediment under laboratory conditions. Nitrous oxide emissions from the treated sediments were measured over three consecutive 24 h periods. This was followed by measurements of iron, manganese, copper and mineral nitrogen species (nitrate and ammonium) mobilisation in the sediments using the diffusive gradients in thin films (DGT) and diffusive equilibria in thin films (DET) techniques and sequential extractions. Increasing copper concentrations are shown to have resulted in significantly reduced nitrate formation near the sediment–water interface and increased nitrous oxide emissions from the sediment overall. The concomitant mobilisation and sequestration of iron with ammonium in the sediment with the highest Cu treatment strongly imply links between the biogeochemical cycles of the two elements. Modest Cu contamination was shown to affect the nitrogen cycle in the tested freshwater sediment, which suggests that even relatively small loads of the metal in fresh watercourses can exert an influence on nutrient loads and greenhouse gas emissions from these environments. [ABSTRACT FROM AUTHOR]

Metal biogeochemistry in the sediment, water, and the sediment–water interface (SWI) was studied in a free water surface constructed wetland. Concentrations of labile copper (Cu), zinc (Zn), sulfate, chloride, and dissolved organic carbon (DOC) were measured with the diffusive gradients in thin film (DGT) and peeper. A good agreement between peeper- and DGT-measured metals was observed for Cu (regression r2 = 0.3, 95% CI of the slopes > 0), but not for Zn (95% CI of the slopes overlapped with 0), which was attributed to the different complexed compounds between Cu and Zn in porewater. The depth profile of labile metals in sediment porewater varied with time and was consistent with the solid-phase metal deposition, showing higher concentrations in the surface layer (3 to − 3 cm) than in the bottom layer (− 4 to − 13 cm). The depth-averaged labile Cu and Zn concentrations measured by DGT were 1.0 and 3.1 µg/L, and labile sulfate, chloride, and DOC concentrations measured by peeper were 1.8, 3.6, and 2.1 mg/L, respectively. A sharp decrease in sulfate occurred in September when sulfate concentrations became the lowest among sampling months. This was caused by the seasonal sulfur cycles in the wetland, where the dominant sulfur reaction is sulfate reduction in warm seasons and sulfide oxidation in cold seasons. Different metal-removal mechanisms were observed in the two wetland cells; sulfur dynamics controlled the removal processes in the cell without frequent disturbance but failed to influence metal removal in the cell with frequent disturbance due to the interruption of anoxic layers. The flux ratios that compare labile element concentrations between the water column and the SWI (R-Cu, R-Zn, R-DOC, R-sulfate, and R-chloride) were generated to determine metal diffusive fluxes at the interface. Labile Zn was mostly transported from the water to the SWI during all seasons (R-Zn < 1 for all months except January). Labile Cu moved from the SWI to the water during the warm months (R-Cu < 1), which was explained by the bioturbation-induced transport of organic matter based on the positive correlations between R-Cu and R-DOC. In general, sediment can serve either as a sink or a source depending on the environmental conditions, metal speciation, and presence of living organisms. Metal flux at the SWI is a key component in the biogeochemical cycling of a constructed wetland. [ABSTRACT FROM AUTHOR]

We used diffusive gradients in thin films (DGT) to measure potentially bioavailable metals in coastal plain streams in the southeastern USA that exhibited strong to moderate blackwater characteristics. Metals were partitioned into particulate metals, DGT-inert metals (i.e., colloidal and refractory organic complexes not accumulated by DGT), and DGT-labile metals (i.e., free metal ions, small inorganic complexes, and labile organic complexes). We also examined the influence of different DGT deployment times using data collected from the field and a follow-up laboratory study. The DGT-measured fraction of dissolved metals in the streams was 15% for Cd, 21% for Zn, 33% for Cu, 37% for Pb, and 98% for Mn. Metals bound to particulates predominated only for Pb. Most of the Cd, Pb, Zn, and Cu were associated with colloids, refractory organic complexes, or particles. Relatively small amounts were in free ion or labile complexes likely to be bioavailable through respiratory surfaces. Modeled concentrations of free and inorganically bound Cu and Pb were lower than the DGT fraction indicating that DGT accumulated some organically bound Cu and Pb that might not have been bioavailable. DGT-exposure times in excess of 5 days may have contributed to the accumulation of partly labile organic–metal complexes and were associated with substantial biofouling that caused metal uptake by DGT to depart from linearity. [ABSTRACT FROM AUTHOR]

In this study, the effects of short-term aerobic conditions on phosphorus (P) mobility in sediment were investigated in the eutrophic lakes. To accomplish this, an indoor cultivation system was established and short-term cultivation (3, 8 and 15 days) was conducted under control and aerobic treatments. High-resolution diffusive gradients in thin films (DGT) and dialysis (HR-Peeper) techniques were used to determine the mobility patterns of P in sediments. The results showed that: (1) Aerobic treatment significantly increased oxygen concentrations (maximum 17.1%) in overlying water within 15 days, with no significant effects on sediment oxygen penetration depth or redox potential. Additionally, aerobic treatment inhibited soluble reactive phosphorus (SRP) and DGT-labile P release from sediment to overlying water. (2) Aerobic treatment decreased the pore water SRP and soluble Fe(II) on day 3 with no impact on sediment SRP/DGT-labile P and soluble/DGT-labile Fe on day 8 and 15. (3) Model simulation using DGT Induced Fluxes in Sediments (DIFS) showed that the pore water SRP replenishment ability of sediment particle P was lower in the aerobic group than the control group, and the sediment system equilibration time was elongated after pore water SRP decreased in the aerobic group on day 3. (4) On day 3, SRP and soluble Fe(II), DGT-labile P and DGT-labile Fe showed significant positive correlations (r > 0.888, p

The reliable sampling of root exudates in soil-grown plants is experimentally challenging. This study aimed at developing a citrate sampling and mapping technique with millimetre-resolution using DGT (diffusive gradients in thin films) ZrOH-binding gels. Citrate adsorption kinetics, DGT capacity, and stability of ZrOH gels were evaluated. ZrOH gels were applied to generate 2D maps of citrate exuded by white lupin roots grown in a rhizotron in a phosphorus-deficient soil. Citrate was adsorbed quantitatively and rapidly by the ZrOH gels; these gels can be stored after sampling for several weeks prior to analysis. The DGT capacity of the ZrOH gel for citrate depends on the ionic strength and the pH of the soil solution, but was suitable for citrate sampling. We generated for the first time 2D citrate maps of rhizotron-grown plants at a millimetre resolution to measure an illustrated plant response to phosphorus fertilization, demonstrating that DGT-based citrate sampling is suitable for studying root exudation in soil environments, at high spatial resolution. The change of binding material would also allow sampling of other exudate classes and exudation profiles of entire root systems. These aspects are crucial in cultivar breeding and selection. [ABSTRACT FROM AUTHOR]

Tidal river networks are affected by the tide and influenced by complex factors related to sediment oxygen demand (SOD). In this study, we used chemical inhibition to measure the oxygen consumption of different types of SOD to explore the specific oxygen consumption mechanism of sediments. Then, we evaluated the diffusion fluxes of the sediment–water interface and factors affecting SOD using diffusive gradients in thin films. Total SOD in the tidal river network area of the Pearl River basin was ∼0.5928 g/m2/day, which was 8.47% higher than that in the non-tidal river network area but lower than that in black and odorous water reported previously. In the tidal river network area, biological SOD was 15.6% higher in summer than in winter, and the difference in total SOD was greatly influenced by human activity. We observed a significant effect of sediment on SOD in winter, whereas there were no significant correlations between sediment and SOD in summer. Different particle-size distributions lead to different organic matter contents, resulting in different biological SOD ratios between seasons. Our study found that seasonal tidal changes can affect ion exchange at the sediment water interface, leading to changes in SOD.These findings will be of great significance for the study of phenomena associated with low dissolved oxygen in tidal river networks and provide directions for future sediment pollution control. [Display omitted] • We evaluated the specific mechanisms of SOD within a tidal river network. • DGT with SOD measurements was used to calculate diffusion flux. • Assessed the effect of the diffusion flux on SOD at the sediment-water interface. • Sediments in TRN area are more easily contaminated than those in the non-TRN areaTides affect the suspended state of sediment. [ABSTRACT FROM AUTHOR]

Cyanobacterial bloom is a pressing issue affecting water supply security and ecosystem health. Phosphorus (P) released from cyanobacterial bloom during recession is one of the most important components involved in the lake P cycle. However, little is known about the consequences and mechanisms of the P cycle in overlying water and sediment due to the anthropogenic treatments of cyanobacterial blooms. In this study, treatment methods using hydrogen peroxide (H 2 O 2), polyaluminum chloride (PAC), and the feces of silver carp were investigated for their influence on the P cycle using microcosm experiments. Results showed that H 2 O 2 treatment significantly increased the internal cycle of sediment-related P, while PAC treatment showed minor effects. H 2 O 2 and PAC treatment suppressed the release of P from sediment before day 10 but promoted the release of P on day 20, while silver carp treatment suppressed the release of P during the whole experiment. The reductive dissolution of iron oxide-hydroxide was the major factor affects the desorption of P. Path analyses further suggested that overlying water properties such as dissolved oxygen (DO) and oxidation-reduction potential (ORP) play critical roles in the treatment-induced sediment P release. Our results quantify the endogenous P diffusion fluxes across the sediment-water interface attributed to cyanobacterial treatments and provide useful guidance for the selection of controlling methods, with silver carp being the most recommended of the three methods studied. [Display omitted] • H 2 O 2 , PAC, and silver carp treatments on P cycle in lake systems were studied. • H 2 O 2 and PAC inhibited P release initially but enhance P release at the end. • Filter-feeding and excretion of algae by silver carp reduced P release. • P release was related to reduction of NaOH–P and changes in DO and ORP. [ABSTRACT FROM AUTHOR]

The diffusive gradients in thin films (DGT) technique serves as a passive sampling method, inducing analyte transport and concentration. Its application is widespread in assessing labile components of metals, organic matter, and nutrients across various environmental media such as water, sediments, and saturated soils. The DGT devices effectively reduce the porewater concentration through irreversible binding of solutes, consequently promoting the release of labile species from the soil/sediment solid phase. However, the precise quantification of simultaneous adsorption and desorption of labile species using DGT devices alone remains a challenge. To address this challenge, the DGT-Induced Fluxes in Soils and Sediments (DIFS) model was developed. This model simulates analyte kinetics in solid phases, solutions, and binding resins by incorporating factors such as soil properties, resupply parameters, and kinetic principles. While the DIFS model has been iteratively improved to increase its accuracy in portraying kinetic behavior in soil/sediment, researchers' incomplete comprehension of it still results in unrealistic fitting outcomes and an oversight of the profound implications posed by kinetic parameters during implementation. This review provides a comprehensive overview of the optimization and utilization of DIFS models, encompassing fundamental concepts behind DGT devices and DIFS models, the kinetic interpretation of DIFS parameters, and instances where the model has been applied to study soils and sediments. It also highlights preexisting limitations of the DIFS model and offers suggestions for more precise modeling in real-world environments. [Display omitted] • DGT technology reveals the kinetic processes of pollutants in soil or sediment. • DIFS model reflects the reservoir and resupply rate of labile analytes. • The limitations and correction approaches of the DIFS model should be considered. [ABSTRACT FROM AUTHOR]

In this study, the effects of short-term aerobic conditions on phosphorus (P) mobility in sediment were investigated in the eutrophic lakes. To accomplish this, an indoor cultivation system was established and short-term cultivation (3, 8 and 15 days) was conducted under control and aerobic treatments. High-resolution diffusive gradients in thin films (DGT) and dialysis (HR-Peeper) techniques were used to determine the mobility patterns of P in sediments. The results showed that: (1) Aerobic treatment significantly increased oxygen concentrations (maximum 17.1%) in overlying water within 15 days, with no significant effects on sediment oxygen penetration depth or redox potential. Additionally, aerobic treatment inhibited soluble reactive phosphorus (SRP) and DGT-labile P release from sediment to overlying water. (2) Aerobic treatment decreased the pore water SRP and soluble Fe(II) on day 3 with no impact on sediment SRP/DGT-labile P and soluble/DGT-labile Fe on day 8 and 15. (3) Model simulation using DGT Induced Fluxes in Sediments (DIFS) showed that the pore water SRP replenishment ability of sediment particle P was lower in the aerobic group than the control group, and the sediment system equilibration time was elongated after pore water SRP decreased in the aerobic group on day 3. (4) On day 3, SRP and soluble Fe(II), DGT-labile P and DGT-labile Fe showed significant positive correlations (r > 0.888, p < 0.001), indicating that reduced pore water SRP concentration was related to decreased pore water soluble Fe(II). [ABSTRACT FROM AUTHOR]

In many cases, stormwater compliance monitoring is labor intensive, expensive, and largely unsuccessful in providing the data needed to support stormwater management goals. To help address these issues, diffusive gradients in thin film (DGTs), time-integrative passive samplers for metals, were evaluated to monitor copper in stormwater runoff. DGTs were co-located with traditional autosamplers within the stormwater conveyance systems at Naval Base San Diego (NBSD) to provide a direct comparison with composite sampling. DGTs were exposed in the laboratory to flow-averaged composite samples from NBSD stormwater conveyance systems. These experiments showed increasing uptake over time (range = 1.5–24 h) for copper, with positive, linear correlations (r2 > 0.980) between exposure duration and copper mass accumulated. However, it appears that the corresponding calculations of the DGT-labile fraction (C DGT) relative to the dissolved fraction fluctuated across the different exposure durations. In general, trends observed for C DGT measurements from the field were consistent with trends in the lab DGT exposures and traditional dissolved metal measurements from composite samples. Finally, time-weighted average copper concentrations from DGTs deployed for the first and second phases of storm events were within 30% of measurements from DGTs that were deployed for the entire storm event in the same stormwater vault. Cumulatively, these results show promise for continuous monitoring with DGTs as an approach that produces data more representative of exposure to the receiving environment during episodic events than data from traditional grab or composite chemistry sampling, and can represent significant cost savings. • DGT data compared well with more resource intensive autosampler derived data. • DGTs consistently measured labile copper in stormwater with exposure durations ≥ 6 h • DGTs measurements of labile copper were consistent when deployed in stormwater vaults. • Simplicity of DGT makes it a logical alternative to traditional stormwater sampling. [ABSTRACT FROM AUTHOR]

In-situ sampling of 2-chlorophenol (CP), 2,4-dichlorophenol (DCP), and 2,4,6-trichlorophenol (TCP) in industrial wastewater was carried out by the diffusive gradients in thin films (DGT) device based on mesoporous carbon (MC). The diffusion coefficients of CP ((1.33 ± 0.05) × 10−6 cm2 s−1), DCP((1.35 ± 0.04) × 10−6 cm2 s−1) and TCP((1.09 ± 0.07) × 10−6 cm2 s−1)) in nylon membrane at 25 °C were independent of pH 3–9 and ionic strength as pNaCl from 0.155 to 3, and were less than their values in water, demonstrating that the nylon membrane with good tolerance and constant diffusion coefficients was suitable as the DGT diffusion layer for controlling the diffusion of CPs. MC-DGT accurately measured the concentrations of CP, DCP and TCP in synthetic solution (C DGT / C SOLN = 0.956–1.04) over the deployment of 120 h. The experimental data also agreed well with the theoretical data calculated on the DGT equation. The performance of MC-DGT for sampling CPs was independent of pH (3–8) and ionic strength as pNaCl (1.3–3) due to the change of the interaction between MC and CPs under relatively high pH and ionic strength. Deployments in laboratory and field trials demonstrated that the MC-DGT was a reliable simple, robust and accurate tool for the in-situ sampling of CP, DCP and TCP in the industrial wastewater. Image 1 • In-situ simultaneous sampling of chlorophenols by DGT based on mesoporous carbon. • Mesoporous carbon from SBA-15 mesoporous silica as template and sucrose as carbon source. • No influence on DGT uptakes for analytes in pH (3–8) and ionic strength (0.001–0.05 mol L−1) ranges. • Positive results proved validity of proposed DGT for in-situ sampling in lab and field trials. [ABSTRACT FROM AUTHOR]

Understanding bioavailable metal behaviour in situ is critical for pollution evaluation and contaminant management in mangrove wetland. Here, the diffusive gradients in thin films technique (DGT) was used for characterizing the (bio)available portions of Cr, Zn, Pb, Cu, Fe and Mn in two mangrove wetlands affected by industrial waste discharges (Jiulong Estuary) and domestic discharges (Zhangjiang Estuary), in Fujian Province, China. In addition, fluorescence excitation emission matrices-parallel factor analysis (EEM-PARAFAC) was applied for characterizing the occurrence and behaviour of dissolved organic matter (DOM) in soil solution, as well as their feasibility for assessing behaviours of metals. The results demonstrated that the combination of DGT and EEM, which are well suitable for studying DOM impacted metal behaviors in mangrove sediments. Discharge of difference wastewater into the mangrove wetlands of Jiulong and Zhangjiang Estuaries, gave rise to the DGT-labile metal concentration of Zn > Cu > Cr > Pb and Zn > Cr > Pb > Cu, respectively. A variety of humic-like fluorescent components was characterized here, providing valuable insights into the chemical composition of DOM in rhizosphere and bulk sediment. Terrestrial humic-like compounds indicated a different binding affinity for heavy metals in mangrove sediments. These findings are useful for the future understanding of the metal speciation and molecular binding mechanisms in such mangrove wetlands. Image 1 • DGT was combined with EEM-PARAFAC method to study metal behaviour. • Humic-like substances were found higher in rhizosphere for metal binding. • Humic substances played a key role in controlling the binding of metals. • Mobility and speciation of metals were related to DOM composition. [ABSTRACT FROM AUTHOR]

Abstract Iron (Fe) and manganese (Mn) reactions have been regarded as the primary factors responsible for the mobilization of phosphorus (P) in lake sediments, although their individual roles are hard to distinguish. In this study, in situ mobilization of P, Fe and Mn in sediments was assessed by high resolution spatio-temporal sampling of their labile forms using diffusive gradient in thin films (DGT) and suction device (Rhizon) techniques. It was found that the monthly concentration distributions showed greater agreement and better correlation coefficients between labile P and labile Fe, than those between labile P and labile Mn, implying that Fe plays a key role in controlling P release in sediments. Furthermore, better correlations were observed between hourly changes in concentrations of soluble reactive phosphorus (SRP) and soluble Fe(II), than those between SRP and soluble Mn. Changes were observed under simulated anaerobic incubation conditions, suggesting that P release was caused by the reductive dissolution of Fe oxides. This was supported by the lack of influences on P release from reductive dissolution of Mn oxides in the sediment-water interface and top sediment layers under the anaerobic incubations. In simulated algal bloom experiments, positive correlations and consistent changes were observed between SRP and soluble Fe(II) concentrations, but not between SRP and soluble Mn concentrations. This further demonstrated the Fe-dependent and Mn-independent release of P in sediments. Therefore, Fe redox reactions have a high impact on P mobilization in sediments, while Mn redox reactions appear to have negligible influences. Graphical abstract Image 1 Highlights • Monthly distribution of labile P concentration correlated with labile Fe concentration in sediments. • Hourly change of SRP correlated with soluble Fe(II) concentrations under anoxic conditions. • Phosphorus was not released during the reductive dissolution of Mn oxides. • Consistent changes in P and Fe but not in Mn occurred in algal bloom sediments. • Fe but not Mn redox reactions should control mobilization of P in sediments. Evidence that Fe redox reactions play a key role in controlling P mobilization in sediments, while Mn redox reactions do not have a significant influence. [ABSTRACT FROM AUTHOR]

Abstract Aluminum-salt inactivating agents are extensively applied to the restoration of lakes polluted by internal phosphorus (hereinafter referred to as "P"). However, there is a lack of micromechanism information regarding the sediment P cycle and its interactions with aluminum salts, which has restricted the engineering applications of aluminum salts. In this study, a sediment core incubation system was used to simulate the influence of aerobic and anaerobic conditions on the effectiveness and stability of aluminum-modified clay (AMC). This study also investigated the millimeter-scale dynamics of P across the sediment-water interface (SWI) using the HR-Peeper and DGT techniques. According to the results, sediment P release mainly occurred under anaerobic conditions. When the incubation system was in an anaerobic state, AMC effectively reduced the internal-P loading. In pore water, there was a positive correlation between soluble Fe and SRP, suggesting that the reductive dissolution of Fe-P constituted the main mechanism of sediment P release. After with dosing AMC, the concentrations of SRP and labile P in the capping layer both dropped abruptly to low levels and the content of Al-P in surface sediments rose, suggesting that AMC had strongly adsorbed phosphates, formed inert Al-P and blocked the phosphate exchange between pore water and overlying water. This study elaborated on the micromechanism of the control of sediment internal P input by AMC and revealed that Al-P precipitation constituted the main mechanism of the inhibition of sediment P release by aluminum-salt inactivating agents. The research findings have a great significance for guiding field applications of aluminum-salt inactivating agents. Graphical abstract Image 1 Highlights • Effects of aluminum-modified clay in inactivating sediment phosphorus were investigated. • Aluminum-modified clay effectively reduced the release flux of sediment phosphorus. • Al-P precipitation constituted the main mechanism of the inhibition of sediment P release by aluminum-modified clay. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • A specific DGT sampler for measurement of nitrophenols in acidic aqueous solutions. • Hazelnut shell-derived activated carbons as DGT binding agents. • No interference of water matrices on the measurement of nitrophenols by DGT sampler. • Reliable results of field deployments in acidic wastewater with relative good precision. Abstract Nitrophenols (such as o-nitrophenol (ONP), p-nitrophenol (PNP), and 2,4-dinitrophenol (DNP)) are priority environmental pollutants. Their toxicity is pH dependent, and these molecular species of nitrophenols exhibit higher toxicity than their anionic counterparts. Herein, for the first time, a method for the in situ measurement of nitrophenols in acidic industrial wastewater was developed using diffusive gradients in thin films (DGT) with lignocellulose hazelnut shell-derived activated carbons (HSACs) as the binding agents. Nylon membranes (0.1 μm rated) with diffusion coefficients of (2.02 ± 0.13) × 10−6 cm2 s−1 for ONP, (1.39 ± 0.09) × 10−6 cm2 s−1 for PNP and (1.20 ± 0.08) × 10−6 cm2 s−1 for DNP at 25 °C were used as the DGT diffusion layers. The accumulation of ONP, PNP, and DNP in DGT samplers based on the HSAC and nylon membranes (HSAC-DGT) agreed well with the theoretical curves predicted by the DGT equation in synthetic solutions with 200 μg L−1 nitrophenol. The uptake of the HSAC-DGT samplers for ONP, PNP, and DNP was found to be independent of the ionic strength of pNaNO 3 (−log [NaNO 3 ] (mol L−1)) in the range of 0.7–3 and the pH range of 3–7 for ONP and PNP and 3–6 for DNP, which is beneficial for their accumulation. The matrices of the tested water samples exhibited no notable interference during nitrophenol analysis by the HSAC-DGT samplers. The results of field deployments in acidic industrial wastewater containing 268.3 ± 79.2 μg L−1 DNP were satisfactorily accurate, thus demonstrating that the HSAC-DGT samplers are good candidates for use in the in situ measurement of nitrophenols in acidic aqueous solutions. [ABSTRACT FROM AUTHOR]

The analysis of mercury in food presents a challenge for analytical chemists. Sample pre-treatment and the preconcentration of mercury prior to measurement are required, even when highly sensitive analytical methods are used. In this work, the Diffusive Gradients in Thin Films technique (DGT), combined with thermal decomposition gold amalgamation atomic absorption spectrometry (TDA-AAS), was investigated for the determination of the total dissolved mercury in fish sauces. Moreover, a new type of binding gel with Purolite S924 resin was used in DGT. Linearity assays for DGT provided determination coefficients around 0.995. Repeatability tests showed a relative standard deviation of less than 10%. pH values in the range of 3–6, as well as NaCl concentrations up to 50 g·L−1, did not affect the performance of DGT. The effective diffusion coefficient of mercury in five-fold diluted fish sauce was determined to be (3.42 ± 0.23)·10−6 cm2·s−1. Based on the 24 h deployment time of DGT, the limit of detection (LOD) for the investigated method was 0.071 µg·L−1. The proposed method, which combines DGT and TDA-AAS, allows for the analysis of fish sauces with mercury concentrations below the LOD of TDA-AAS, and significantly reduces the wear and corrosion of the TDA-AAS components.

Abstract A new theoretical method was established for the combinatorial calculation of the dissociation rate constant (K -1) of the metal-organic complexes (MLs), the concentration of free ionic soil metals (C M), the labile concentration of soil metal-organic complexes (C ML) based on diffusive gradients in thin-films (DGT) technique with a range of diffusive layer thicknesses (0.053–0.173 mm) in soils. The fitting results agreed well with the determined values. The values of K -1 , C ML and C M were calculated without other morphological analysis software and the fitting results agreed well with the determined values with some advantages such as the use of fewer hypothetical parameters, ease of calculation, the full embodiment of the contribution of MLs to the labile content. According to the results of model fitting, cation exchange capacity and soil organic matter were found to be the key environmental factors for K -1 values of Cd and Ni, respectively. The labile contents of Cd and Ni in soil were closely related with pH, soil organic matter and the total contents of heavy metals. Highlights • A new theoretical calculation for the dissociation rate constant of metal-organic complexes. • Diffusive gradients in thin films technique based on with a range of diffusive layer thicknesses. • The fitting results agreed well with the determined values. [ABSTRACT FROM AUTHOR]

Abstract The diffusive gradients in thin films (DGT) technique has been used routinely for monitoring the dissolved, bioavailable fraction of trace metals in freshwater during field campaigns. Nevertheless, for long deployment times, the biofilm formed on the filter of the DGT devices restricts trace metal uptake and hence interferes with the DGT measurements. In this work, we design different experiments to evaluate the potential of silver nanoparticles (AgNPs) in preventing the formation of biofilms on in-house manufactured mercury-specific DGTs. Laboratory tests were carried out by a microcosm system in independent glass containers, where biofilms obtained from field inocula were grown for weeks. Afterward, several experiments were performed with Hg-spiked river water, biofilms and DGTs treated and untreated with AgNPs to better understand biofilm colonization, inhibition and Hg uptake. The results showed that the treatment is very useful, since the mass of the biofilm accumulated at the surface of the treated DGT is significantly (p < 0.05) lower than in control (untreated) devices. Tests in colonized environments and Hg-spiked river water showed that the Hg uptake by the treated DGT matched the theoretical values and prevented biofilm formation up to 24 days post-deployment. Conversely, in deployments longer than two weeks using the untreated DGT, measurements could be underestimated by 35%. The results in the field reveal that in sampling stations with high levels of suspended matter, the filter becomes clogged despite there being no biofilm, thereby explaining its low efficiency for the uptake of Hg. In summary, the use of AgNPs inhibits biofilm formation and their use is especially recommended in eutrophic freshwaters with low amounts of suspended particulate matter. Graphical abstract Image 1 Highlights • Microcosm tests proved that biofilm growth affects normal Hg diffusion through DGT. • Untreated DGTs efficiently monitor labile Hg concentrations for up to 8–10 days. • For longer field deployments, the biofilm reduces drastically the Hg uptake by 35%. • DGT treated with silver nanoparticles inhibits biofilm without a loss in diffusion rate. • Antibiofouling treatment does not affect the accurate measurement of the Hg by DGT. [ABSTRACT FROM AUTHOR]

The effect of exogenous phosphate (P, 200 mg⋅kg −1 soil) on the lability and phytoavailability of arsenic (As) was studied using the diffusive gradients in thin films (DGT) technique. Lettuce were grown on the As-amended soils following the stabilization of soil labile As after 90 days incubation. Phosphate (P) application generally facilitated plant growth except one grown on P-sufficient soil. Soil labile As concentration increased in all the soils after P application due to a competition effect. Plant As concentration increased in red soils collected from Hunan Province, while decreases were observed in the other soils. Even though, an overall trend of decrease was obtained in As phytoavailability along with the increase of DGT-measured soil labile P/As molar ratio. The functional equation between P/As and As phytoavailability provided a critical value of 1.7, which could be used as a guidance for rational P fertilization, thus avoiding overfertilization. [ABSTRACT FROM AUTHOR]

The South-to-North Water Diversion Project has been initiated to address the problem of water shortages in north China. However, the environmental impact of this project is currently unclear, especially for the geochemical process of toxic trace metals in reservoir riparian soil following water submergence. The mobility of Ni in Miyun Reservoir riparian soil samples was investigated using diffusive gradients in thin films (DGT), considering five different land use types and three vertical elevations. The DGT-induced fluxes in soil (DIFS) model was applied to simulate the kinetics of Ni mobilization in the soil. The results showed that the average concentration of Ni was 36.58 mg/kg, which was slightly higher than the corresponding background values reported for both Beijing and China. Coincidentally, the highest concentrations of both total Ni and DGT-labile Ni (C DGT -Ni) were observed at the same site (recreational area), indicating that anthropogenic activities may have contributed to the release of Ni. Land use type and vertical elevation had no significant influence on C DGT -Ni. In addition, C DGT -Ni was positively correlated with reducible fraction, C DGT -Fe, C DGT -Mn, and TOC, indicating that Ni in the soils was adsorbed mainly on the Fe/Mn oxides and organic matter. Moreover, the low values of R (C DGT -Ni/C sol -Ni, R < 0.25) indicated that the replenishment of Ni from the solid phase was poor, and the rate of Ni desorption was considerably lower than its depletion rate, thus leaving only a small proportion of Ni was available. [ABSTRACT FROM AUTHOR]

Extractive tests for determining the plant-availability of soil phosphorus (P) give varying results due to the inherently different characteristics of the extraction solution. Generally, classical soil P tests such as the Olsen or calcium acetate/lactate (CAL) method do not give an indication on the total amount of plant available P, but merely give an indication of the equilibrium between soil and extraction solution. It is also not entirely clear which fractions of P are directly determined through the various methods of extraction, i.e., determined P must not be immediately plant available, as is the case for rock phosphate. It is therefore possible that extraction methods either over or under estimate the amount of P available for plant consumption. In this research, we compared three methods of soil P determination (CAL, Olsen and diffusive gradients in thin films (DGT)) with regards to their ability to determine P species (Ca(H2PO4)2, CaHPO4, Ca3(PO4)2 and Inositol-6-hexakisphosphate) added to soils of high sorption capacity, immediately after as well as two weeks after application. For each of the methods, it could be shown that sorption processes in the soil immediately (0 days incubation) fix P to a point where it is not extractable through any of the described methods. These sorption processes continue over time, leading to a further decrease of determined P. The acidic CAL extraction method gives higher results of extractable P compared to the Olsen method. Due to the extraction of Ca3(PO4)2, the CAL method may overestimate immediately plant-available P. The most suitable methods for the determination of immediately plant available P may therefore be the Olsen and DGT methods. Organic IP6 is not determined by any of the extraction methods. At low concentrations of soil P, the DGT method may fail to give results.

Elution of Chelex® binding layers, commonly used for the diffusive gradients in thin films technique (DGT), is recognized as the most important contributor to the uncertainty of DGT measurements. Limiting uncertainty requires the use of optimized procedures and suitable elution recoveries ( f ). This work therefore investigated elution robustness to propose improved strategies. A wide range of conditions were investigated for the main elution parameters (Chelex® particle size, elution time, Chelex® loading, and eluent concentration and volume) on Al(III), Cd(II), Co(II), Cr(III), Cu(II), Ni(II), Pb(II), and Zn(II). Results showed that the choice of elution conditions should be a compromise driven by study constrains in terms of accuracy, repeatability, sensitivity, and targeted elements. Using experimentally determined recoveries should improve accuracy by approximately 5 to 10% compared to the use of recoveries from the literature. Fast elution of 1 h can be achieved without significant loss of recovery and repeatability except for Cr(III) (8 h minimum). Elution recovery depended on Chelex® loading for Zn and Cr and introducing recoveries adapted to the loading could improve accuracy up to, respectively, 11 and 27%. When standard recoveries are used, a 0.85 f value would be more appropriate than the common value of 0.8 to minimize inaccuracy (except for Cr). Some flexibility can be applied to elution conditions without a significant change in recovery for most elements: HNO concentration of 1-15 M, volume of 1-2 mL, duration of 8-48 h. Cr(III) was unique in its sensitivity to elution condition variations; thus, choice is more restricted for this element. [ABSTRACT FROM AUTHOR]

The DGT technique (diffusive gradients in thin films) is widely used for passive sampling of labile trace metals and metalloids in natural waters. Although development of fouling on the protective membranes is frequently observed, its effect on DGT sampling has been barely investigated. This study evaluates the influence of fouling on sampling of trace cationic metals Cd(II), Cu(II), Ni(II) and Pb(II) and oxyanions As(V), Cr(VI), Sb(V) and Se(VI). Fouling was developed in situ on polycarbonate membranes in four diverse natural freshwater environments and sampling alteration was assessed in controlled laboratory experiments. Accumulation of oxyanions and Ni was unaltered in the presence of fouling whereas significant alteration occurred in sampling of Cd, Cu and Pb (at pH ∼5.4). Characterization of the fouled membranes highlighted the intervention of sorption phenomenon as sampling alteration was systematically observed alongside element sorption onto fouled membrane. A preliminary flowchart for identifying potentially biased quantifications linked to fouling development during in situ DGT deployment in natural waters is proposed. [ABSTRACT FROM AUTHOR]

Uptake of selenium (Se) by plants largely depend on the availability of Se in soil. Soils and plants were sampled four times within 8 weeks of plant growth in pot experiments using four plant species. Sequential extraction and diffusive gradients in thin-films (DGT) method were employed to measure Se concentrations in potted soils in selenite- or selenate-amended soils. Results showed that DGT-measured Se concentrations ( C DGT −Se) were generally several folds higher for selenate than selenite amended soils, which were obviously affected by the plant species and the duration of their growth. For example, the folds in soil planted with mustard were 1.49–3.47 and those in soils planted with purple cabbage and broccoli, which grew for 3 and 4 weeks after sowing, were 1.06–2.14 and only 0.15–0.62 after 6 weeks of growth. The selenate-amended soil planted with wheat showed an extremely high C DGT −Se compared with selenite-amended soil, except the last harvest. Furthermore, minimal changes in C DGT −Se and soluble Se(IV) were found in selenite-amended soils during plant growth, whereas significant changes were observed in selenate-amended soils ( p < 0.05). Additionally, Se distribution in various fractions of soil remarkably changed; the soils planted with purple cabbage and broccoli showed the most obvious change followed by wheat and mustard. Soluble Se(VI) and exchangeable Se(VI) were likely the major sources of C DGT −Se in selenate-amended soils, and soluble Se(IV) was the possible source of C DGT −Se in selenite-amended soils. In selenate-amended soils, soluble Se(VI) and exchangeable Se(VI) were significantly correlated with Se concentrations in purple cabbage, broccoli, and mustard; in wheat, Se concentration was significantly correlated only with soluble Se(VI) but not with exchangeable Se. C DGT −Se eventually became positively correlated with Se concentrations accumulated by different plants, indicating that DGT is a feasible method in predicting plant uptake of selenate but not of selenite. [ABSTRACT FROM AUTHOR]

Biochar application to agricultural land has been proposed as a means for improving phosphorus (P) availability in soil. The purpose of the current study was to understand how pyrolysis temperature affects P speciation in biochar and how this affects availability of P in the amended soil. Biochar was produced at different temperatures from digestate solids. The primary species of P in digestate solids were simple calcium phosphates. However, a high co-occurrence of magnesium (Mg) and P, indicated that struvite or other magnesium phosphates may also be important species. At low temperatures, pyrolysis had little effect on P speciation; however, as the temperature increased above 600 °C, the P gradually became more thermodynamically stable in species such as apatite. At very high temperatures above 1000 °C, there were indications of reduced forms of P. Biochar production decreased the immediate availability of P in comparison with the original digestate solids. However, for biochar produced at low temperatures, availability quickly increased to the same levels as in the digestate solids. For biochar produced at higher temperatures, availability remained depressed for much longer. The low availability of P in the biochar produced at high temperatures can probably be explained by the formation of less soluble P species in the biochar. In contrast, the transient decrease of availability of the P in the biochar produced at low temperatures can be explained by mechanisms, such as sorption on biochar, which gradually decreases because of oxidation of the biochar surfaces or changes in pH around the biochar particles. [ABSTRACT FROM AUTHOR]

A diffusive gradient in thin films (DGT) technique, based on a strongly basic anion exchange resin (Amberlite IRA-400), was successfully tested for S/S analysis in labile soil sulfate. Separation of matrix elements (Na, K, and Ca) that potentially cause non-spectral interferences in S/S analysis by MC ICP-MS (multi-collector inductively coupled plasma-mass spectrometry) during sampling of sulfate was demonstrated. No isotopic fractionation caused by diffusion or elution of sulfate was observed below a resin gel disc loading of ≤79 μg S. Above this threshold, fractionation towards S was observed. The method was applied to 11 different topsoils and one mineral soil profile (0-100 cm depth) and compared with soil sulfate extraction by water. The S amount and isotopic ratio in DGT-S and water-extractable sulfate correlated significantly ( r = 0.89 and r = 0.74 for the 11 topsoils, respectively). The systematically lower S/S isotope ratios of the DGT-S were ascribed to mineralization of organic S. [ABSTRACT FROM AUTHOR]

The Diffusive Gradients in Thin Films (DGT) technique using PIWBA resin (The Dow Chemical Company) was developed and validated for the measurement of uranium (U) concentration in natural and uranium mining influenced waters. The U uptake on the PIWBA resin gel was 97.3 ± 0.4% (batch method; V sol = 5 mL; [U] = 20 μg L −1 ; 0.01 M NaNO 3 ; pH = 7.0 ± 0.2). The optimal eluent was found to be HNO 3conc /70 °C with an elution efficiency of 88.9 ± 1.4%. The laboratory DGT investigation demonstrated that the PIWBA resin gel exhibits a very good performance across a wide range of pH (3–9) and ionic strength (0.001–0.7 M NaNO 3 ) at different time intervals. Neither effect of PO 4 3− (up to 1.72 × 10 −4 M), nor of HCO 3 − (up to 8.20 × 10 −3 M) on the quantitative measurement of uranium by DGT- PIWBA method were observed. Only at very high Ca 2+ (2.66 × 10 −4 M), and SO 4 2− (5.55 × 10 −4 M) concentration, the U uptake on DGT- PIWBA was appreciably lessened. In-situ DGT field evaluation was carried out in the vicinity of three former uranium mining sites in France (Loire-Atlantique and Herault departments), which employ different water treatment technologies and have different natural geochemical characteristics. There was a similar or inferior U uptake on DGT-Chelex ® -100 in comparison with the U accumulation on a DGT- PIWBA sampler. Most likely, the performance of Chelex ® -100 was negatively affected by a highly complex matrix of mining waters. The high concentration and identity of co-accumulating analytes, typical for the mining environment, did not have a substantial impact on the quantitative uptake of labile U species on DGT - PIWBA . The use of the polyphenol impregnated anion exchange resin leads to a significant advancement in the application and development of the DGT technique for determination of U in the vicinity of the former uranium mining sites. [ABSTRACT FROM AUTHOR]